Complex metal compound of polyhydroxy benzene derivatives and process of making it



Patented Jan. 22, 1935 'DROXY BENZENE" DERIVATIVES rnocmss-or mmnerv Hans schmiaetvohwihkeli, near: ltlbertelieGer many, assignor: to: Winthrop I Gheminal: Gompanx; Inc New York, wm

N. Y ma, corporation of I in Drawing. nppumn retmr mueesise.

a minim-15458933 Inn Germany:

The present invention relittesiio new complex metal saltsoipolyhydroxynom'poundsof benzene derivatives. contaiiiii'ngc at least twoihydroxy groups. in-ort1iov-positionand toeapprocess of -pnei -paring tm same. i V

Complex. metal. saltsiofi' poly-hydi oxy benzene compounds: containing, at. least. two l yd 'ox y.T groups inioistho positionnani etleasti one acid. g 'ougflth'eLhydrogen .-a,tom-,of.- which-may be i re- 1% pliatcedlby arm-alkali metal," and a metaL capable oLTb'eing converted from a, lower a. higherstage (at oxidation, "have. been described--- he eto fbreibn-example; in ll-KS. Patents Nos; 1,51%),154 t. 1,-71'8;492',.,and;1,718,493. v

15,:- lnachordance withflthepresent invention, the

abbize: mentioned complexfioompounds are; conevertemhy theactionot. oxidizing-agentszinto new products. Various oxidizing agentsT qanibe. einrf ployed forn example hydrogen peroxide, mag- 201 nesium.pemxide, sodium per-sulfate andatheilike. Iiisome instances, it. 'possibleato useeeles; mentarm oxygen. y The: oxidatiomis: generally ef fectedLinrsolutioni The'solutionscontni-ning the newcompoungis a,i:e .eva,;:voreted on the new com.-

pounds are. precipitated means ref-La: suitable. r ani'emedium -ei g methad-- a.;coho1.= Insomei cases .the. complexncompounds -may' be oxidized= in theinsolideformw The new compoundslare generallwcoloned pqw" 30 dersfisoluble.inswateniand generalm armless than the unoxidized compounds Vi The following,- examples wiileillustr-ate:

vention -withoutJ1imitingsit,thereto-:- i k dii-l-pyrocatechin-disulfonate) are treated; with;

121QGS.:"0f :hdIQE8IIperoxide ofz3% strength;aneu.-- tralized. with dilute caustic potash and evapnrated: residuei'fromu evaporatinmz. dissolves Q iemiiiyrim water "and contains-antimony i'mits:

pentavalent form no furtherabsorptiom of id dine). If desired? the residue can be re-dissolved in water; neutralized with 'dflute causticpotiatsh and precipitatedby pouring into-methyPaJ-cohol;

Example 2."-12 grams of potassium stannous pyrocate'chin' disulfonateane dissolvediihi'OU'ecs: ofwater. and-Ha rapid? current of. air is 'passed through'puntilliahtestlportion diluted with water, no Ringer ebsorhs. i'odi'ne; The. solution etlien 50;- evaporated l Theires'idue is.a comp1fe compound.-

of! tetravalent. tun-which readi1y= moms; waten. e

Eran 1402b 39-20 .gramsoithe-potassium s'altoflf m'anganesepynocatechin, .disulfonicflaeid areL selvedi'in 100. ccs.. of water andLthroughvthis so lutioni ahstiiongvcurrent ofu air is passedl during. at; least- 24 hours. Themthe .sol'ut ion isqpounedg into emethyllraleohol thezpzecipitated inew come poundisfiltereil. washed. \withtmethyl a1cohoLand., driedjnia-n exsi'ccator. It is a darkcoldrdQpow: Q: derueasily soluble inflwater withua. greenish col oration; v

Enample 4.-8L g 'a.msof, the potassium-salt of the.v antimony. diz- (pyrogalloldisulfonio acidi are suspended. in 80 ccs. of water, andea l mixtunee of. 24- grams oi. hydrogen, pero id'e and. 24L ees", 6:; water. is added on stirring dissolves. Afters seine time. thesolutibn, is neutralized with diluted; caustic potnshe soliitiongffilier ed and theinew comm -20. comnoundjdfl the pentvalent antimonwigprer cipitatedi by pouiiing the solution a into; methgle alcohol. The reaotion piiobablmproceedsaccord;1 ing to the following equation:

mm CIKFI q The newff comjilex. compound? a,. yellbi 40 p0Wdr2easi1yso1i1b1e Water rfi'fom. it T is. not precipitated lhy, caustio (social. solution ori y hydrochloric acid? It is a. therapeutiiiafiy valu -,1 able substance especially against. infectious-e eases. .7

Efc'ampl 5.I15;14 Tgrams of. protocatecliuicheicidl and 10' "grams offantimony. oxid'e a te vdiss'oliielzll'iii. 50 cos. 0L2. fli'diethylhmine"solutibnebynbbiling' andneutialfzi'ngwitliahhutil'ccsflofiN diethylamine. solution" T'dithe filtredsoliitibiewhilij 50 contains the diethylamine salt of the antimony protocatechuic acid, 9 grams of hydrogen peroxide are added. The solution is neutralized with diethylamine solution and evaporated. The new complex compound of the pentavalent antimony is a yellowish powder, easily soluble in water.

Example 6.-10 grams of the sodium salt of tin protocatechuic acid are dissolved in'- 100 cos. of water. Subsequently a. strong current of air is passed through the solution for some hours, and

then the solution is evaporated. The complex compound of the tetra-valent tinis a ,pale co lored substance, easily soluble in water;

In an analogous manner'compl'ex "compounds "drQXy"groups' in:ortho position to each other,

and.o1f,-a metal selected from the group consistof the said polyhydroxy benzenes with other; metals which can be converted-into a higher stage of oxidation, for example,farsenic,==iron" andjvaei."

nadium, can be oxidized to rormmew organic metal complex compounds. Since the oxidation of the trivalent antimony. i compounds;-,.alwayS.

leads to pentavalent antimony'compounds which are of a higher degree of acidity than the triva lent antimony compounds, the oxidation product i in Example, ,1 was neutralized with awater-soluble alkali as all of the products, 'accordingto the present invention, are intended for practical useonly'in the"completely neutralstate. The tin and manganese compounds'obtainable according, to the above examples are not changed in acidity and consequently do not need to be neutralized Whether ornot the oxidation prodf' uct must be neutralized in order to obtain a neuj tral product, depends upon the amphoteri'c character of the metal contained therein. "It 'isfobs" vious that the arsenic compounds may require a subsequent neutralization as described with'reference to the antimony compounds, "whereas the iron compounds do 'not require such neutralization; R

The second neutralization step described in Examplel is-carried out because, on redissolution of the product'inwaten'some polymerization 00- curs as isusual with compounds of pentavalent antimony, which is suppressed by adding a little alkali, the polymerization being usually ascer-" tained by the fact that an 'aqueous solution'of r j ofa metal of-thegroup consisting of antimony, tin, arsenic, -;iron,-vanadium and manganese, said the product becomes slightlyflaz zid. 1 I claim:

1. The process whichicomprises treating a .metal complex salt of poly-hydroxy-benzenes of the general formula: a

wherein X meanshydrogen, or a hydroxyl group, and at least one Y an acid reacting substituent capableof forming a salt, with hydrogen peroxide and neutralizing the reaction mixture. I

2. The process which comprises treating; po-

tassium antimony di-(pyrocatechin-disulfonatelwith hydrogen peroxide and: neutralizing the re-f action mixture with a water-soluble alkali;

3. 'The process which c ompri'ses'treating' potas ,L The process whichcomprisestreatin potas of'antimo'n'y, tin, manganese, arsenic, iron andvanadium, which metal is present in a lower stage} ofoxi'dation'and attached to at least one of-"'s'aid-polyhydroxy benzene nuclei through the oxygen atoms'of'the'two hydroxy groups standing-inf-ortho-position to each other, the polyhydroxy benzene nucleus furthermore containing at least one acid group,=the hydrogen atom of which may be replaced by an alkali metal, and neutralduce a neutralproduct; I v I '7. The process which comprises treating. with.

izing the reaction mixture if necessary to proan oxidizing agent a complex organo metallic compound composed of at least "one polyhydroxy benzene nucleus which contains at least two hydroxy groups in ortho-position to each other, and of'a metal of the group consistingof an timony, tin, arsenic, iron, vanadium and manganese, said metalbeing in' a lower stage of oxidationjand attached to at least one of the said polyhydroxy 'ibenzene nuclei through the oxygen atoms of the" two hydroxy groups standing in. ortho-position to each "other," the 'polyhydroxy. benzene nucleus furthermore containing at least" one acid group, the'hydrogen' atom of which may be replaced by an alkali metal, and neutralizing the re'action mixture if necessary to produce a neutral-'pioduct."-" 'j 8. A salt or-a complex organo metallic compound being composed of atleast one polyhydroxy benzene nucleus which contains at least two hy" droxy groups in ortho-position' toeach other, and

metal being in its-higher stage of oxidation and attached to atleast one of the said polyhydroxy 1 benzene nuclei through the oxygen atomsof the two hydroxy groups standing'inortho-positi'on to-each' other, the" polyhydroxy benzene nucleus furthermore containing at least one acid group, the hydroger'r atom of which is replac'ed'b'y" an'=all 'ali--metal, which product is 'a-colored'powder soluble in wateranda therapeutically valuable substance 'which is generally less toxicthan the corresponding -metal complex compounds containing the metal in a lower stage of oxidation.u-

w. v 9.;1'A salt of acomplex organometallic com-r pound which is composed of at least one poly-v hydroxy benzene nucleusv which contains at least two hydroxy groups in ortho-position to each other, and of tin, beingin .its higher stage 01 oxidation and attached to at least one of. the. saidpolyhydroxy benzene nuclei through the oxygen atomsof the two hydroxy groups standingin ortho-p'osition to each other,j the polyhydr'oxy benzene nucleus'furthermorel'containing at least one acid group, the hydrogen atom o'fwhich is replaced by an'alkali metal, which product is a' whitish powder soluble in water and a there.-

through the oxygen atoms of the hydroxyl groups peutically valuable substance which is generally less toxic than the corresponding metal complex compounds containing the metal in its lower stage of oxidation.

10. An alkali metal salt of a complex organo metallic compound which is composed of at least one molecule of pyrocatechin disulfonic acid and of tin, being in its higher stageof oxidation and attached to the said pyrocatechin sulfonic acid thereof, which product is a whitish powder soluble in water and a therapeutically valuable substance which is generally less toxic than the cor-' fonate, which is a whitish water soluble powder.

HANS SCHMIDT. 

